Comparing Density Functional Theory Metal-Ligand Bond Dissociation Enthalpies with Experimental Solution-Phase Enthalpies of Activation for Bond Dissociation.

The predictive ability of density functional theory is fundamental to its usefulness in chemical applications. Recent work has compared solution-phase enthalpies of activation for metal-ligand bond dissociation to enthalpies of reaction for bond dissociation, and the present work continues those comparisons for 43 density functional methods. The results for ligand dissociation enthalpies of 30 metal-ligand complexes tested in this work reveal significant inadequacies of some functionals as well as challenges from the dispersion corrections to some functionals. The analysis presented here demonstrates the excellent performance of a recent density functional, M11plus, which contains nonlocal rung-3.5 correlation. We also find a good agreement between theory and experiment for some functionals without empirical dispersion corrections such as M06, r2SCAN, M06-L, and revM11, as well as good performance for some functionals with added dispersion corrections such as B97X-D (which always has a correction) and BLYP, B3LYP, CAM-B3LYP, and PBE0 when the optional dispersion corrections are added.

Brothers, E. N., Bengali, A. A., Scalmani, G., Janesko, B. G., Verma, P., Truhlar, D. G., & Frisch, M. J.

Brothers, Edward N||Bengali, Ashfaq A||Scalmani, Giovanni||Janesko, Benjamin G||Verma, Pragya||Truhlar, Donald G||Frisch, Michael J

Comparing Density Functional Theory Metal-Ligand Bond Dissociation Enthalpies with Experimental Solution-Phase Enthalpies of Activation for Bond Dissociation. Academic Article